CS212332B2 - Fungicide means - Google Patents

Abstract

New, substituted cyanamides, processes for the manufacture thereof, and fungicides containing these compounds.

Description

The invention relates to novel valuable substituted cyanemides, to a process for their preparation, and to fungicidal compositions containing these compounds as active substances.

It is already known that cyanacetamide derivatives, for example 2-cyano-N-ethylamino-carboin-2-methoxyiminoacetamide, exhibit fungicidal activity for 1 lower fungi (see U.S. Patent No. 3,954,992). It is further known that N-trichloro-4-ethoxy-1H-tetrafluoro-tetrafluorophenamide is used to combat fungi (see Chemcl. Week, June 21, 1972, p. 46).

It has now been found that the substituted cyanamides of formula (I)

^ co-OCH ₃ CN (I) wherein R1 is methyl or ethyl 'group,

R ² is methyl or ethyl and r 3 is C 1 -C 4 alkyl optionally substituted by chlorine or methoxy, C 3 -C 6 cycloalkyl, phenyl optionally substituted by fluorine, a thienyl, furyl or isoxazole moiety showing good fungicidal effect for those phytopathogenic fungi.

Next. It has been found that the substituted cyanamides of the above general formula (I) can be obtained by obtaining a compound of the general formula (II).

_X CH ₂ -Hal ^X CO-R ³ (II) wherein r 1, R ² and r ² are as defined above, and

Hal represents a halogen atom, in particular chlorine or bromine, and reacts with the acid of formula III

(III) wherein

M represents a hydrogen atom, an alkali metal or a tetraalkyl alkyl group, optionally in the presence of an acid binding agent and optionally in the presence of a solvent inert to the reactants.

The above reaction may be carried out in the absence of solvents or in the presence of solvents inert to the reactants. Suitable solvents are, for example, aromatic hydrocarbons, such as toluene or xylene, halogenated hydrocarbons, such as chlorobenzene, chloroform, methylene chloride or methyl chloride, ethers, decahydrohydrofurene or dioxane, nitriles, such as acetoacetyl, N, N-dialkyl amide, such as dimethyl sulfoxide, ketones such as acetone, aliphatic acid esters such as ethyl acetate, and mixtures of these solvents. The reaction temperatures are between 0 and 150 ° C, preferably between 20 and 100 ° C.

As the starting material, the cyenamide of the above-mentioned general formula (III), in which M is hydrogen, is preferably used in the presence of an acid-binding agent. Suitable agents are tertiary amines, for example triethylamine. pyridine and substituted pyridines, or inorganic bases, for example alkali metal oxides, hydroxides, carbonates and bicarbonates.

In accordance with a particularly preferred embodiment of the process for the preparation of the cyanomine compounds of the formula I, the N-halomethyl chloride of the formula II

(II) in which

3

R, R, and R. mmj as defined above and

Hal is chlorine or bromine, reacted with the kynnamide of formula III

(III) wherein

M is an alkali metal, in a two-phase system, where one phase is water, and the other phase is a solvent immiscible with the aqueous phase, inert to the reactants, in the catalyst of the phase transfer catalyst. Alternatively, the reaction may also be carried out in a two-phase system in the presence of a phase transfer catalyst without the addition of water, in which case the acid of formula III is suspended in a water-miscible solvent.

The water solvent is preferably an aromatic hydrocarbon or halogenated hydrocarbon. The phase transfer catalyst is used, for example, in an amount of from 0.5 to 30 moles. %, based on the N-halogenomethylolol of formula II used.

The reaction is carried out at a temperature of 0 to 100 ° C, preferably 10 to 50 ° C.

Possible phase transfer catalysts are onium deelvates, for example quaternary lonium compounds or phosphonium compounds, or moleoyl poles ethers. Suitable quaternary ammonium compounds include tttraSjtylmlOOiumh'ldooenoujOát, tetrapeotlllmcniumhhooid, tetгQoktylιmooijmchhorid, tгipropllbutyamюnijmchhorie, leotards 1x1-- © ΙιΙι-oninumhhoold, hexadecyl · trimttylmюoijmohhorie, eisteaJyf-object! Lelylmlooijlm ¢ hhorie, dibenzylei-etlllшonOшmmítylsujfát, dimetyldodehlO-benzylιmooiumchhorie, Senoyltri-eeyilmoo0ijmhhloid,. Senzyltriylmlooliminoorphorium, 2-dimethylethyltriethylethylmoniumcorium, and examples of quaternary phosphonium compounds include tri-butyl-ethylphosphoric acid, hexaethylsilyltrifluorophosphonium phosphonium phosphonium phosphonium phosphonium bromide, and the like. ‘

Macrocyclic polyethers are, for example, 15-crown-5, 18-crown-6, dibenzo-18-crown-6 and dicyclohexyl-18-crown-6 (crown-ethers).

For the preparation of the novel compounds, at least 1 mole of the cyanamide (III) is used per mole of N-halomethylanilide (II).

The isolation of the compounds of the formula I is carried out, for example, by optionally filtering off the halide formed from the reaction mixture, evaporating the filtrate and dissolving the residue in a water-immiscible organic solvent. The organic phase is then washed with water and, after drying, evaporated in vacuo. The product of the formula I obtained is in many cases pure, but if necessary, it can be further purified by recrystallization or chromatography, for example on silica gel.

In the biphasic process, after the reaction is complete, the organic phase is separated off, optionally freed from the insoluble matter by filtration, washed with water, dried and the active compound of the formula I isolated as described above.

The N-halomethylanilides used as starting materials are partially known (see U.S. Pat. No. 3,637,847) or can be prepared in a manner known per se by reacting appropriately substituted phenylazomethines with the acid chlorides of the general formula R R-CO-Hal, where R ^ has the and Hal represents a halogen atom.

The cyanamide derivatives of formula (III) are known compounds. By way of example, cyanocarbamic acid methyl ester can be mentioned (see German Patent Specification No. 24 74 453, DOS No. 17 95 849).

Examples of suitable cyanamide derivatives used as starting materials are cyanocarbamic acid methyl ester or its sodium, potassium or tetramethylammonium salt.

The following examples illustrate the preparation of the novel cyanamide derivatives of the formula (I) as well as the preparation of the starting materials of the formula (II).

The relationship of parts by weight to parts by volume in the examples corresponds to that of kilograms to liters.

Example

To a solution of 130.5 parts by weight of 2-furancarboxylic acid chloride in 100 parts by volume of toluene, 315 parts by volume of a toluene solution containing 1 mol of 2,6-dimethylphenylazomethine (see U.S. Pat. 637 847). The reaction mixture was stirred at room temperature for 10 hours, then cooled, filtered off with suction and dried in vacuo. 198 parts by weight of 2-furancarboxylic acid K-chloromethyl-2 *, 6 * -dimethylanilide having a melting point of 124 DEG-126 DEG C. are obtained.

The following N-halomethylanilides of formula II can be prepared in an analogous manner:

fl?

^ CH2-Hal

R ¹ R2 Hal r3 Melting point (° C) ch ₃ CH3 CL CH3 solid matter ^CH 3 C ₂ H ₅ Cl CH ₃ solid matter ^C 2 ^H 5 c ₂ h ₅ CL CH ₃ oil CH ₃ CH3 CL C ₂ H ₅ oil CH ₃ ^С Л G1 ^C 5 ^H 5 oil ^C 2 ^H 5 C2H5 CL ^C 2 ^H 5 oil ^CH 3 CH3 CL CH _{(CH3) 2} ch, c ₂ h ₅ C3 CH _{(CH3) 2} ^CgHg C2H5 Cl CH _{(CH3) 2} 75 to 76 ^C 2 ^H 5 c ₂ h ₅ CL С (СН ₃ ) з oil CH3 CH3 Cl CH (C1) CH ₃ 95 C2H5 ^CH3 CL СН (С1) С ^C 2 ^H 5 ^C A CL СН (С1) С CH3 ^C 2 ^H 5 CL CH2-CH2Cl viscous oil CH3 ch ₃ CL C 1 -C 4 Cl CH3 CH3 CL CH2-CH2-CH2Cl CH3 CH3 Cl CHO1 ₂ 102 to 104 CH3 ^C 2 ^H 5 CL CHCC-2 88 to 90 CH3 Cl CC1 ₃ oil CH3 CH ₃ Cl 0 82 CH3 ^C 2 ^H 5 Cl < oil ^C 2 ^H 5 ^C 2 ^H 5 CL 0 oil

212332 6 continued table

R ¹ R ² Hal R ³ Melting point (° C) CH 2 ^CH 3 Cl O CH 2 ^CH 3 Cl 0 ^CH 3 ^C 2 ^H 5 Cl 0 c ₂ H ₅ ^C 2 ^H 5 Cl 0 97 to 100 CH ₃ ch ₃ Cl CH ₂ OCH ₃ 70 ^CH 3 ^C 2 ^H 5 Cl CH ₂ OCH ₃ ^C 2 ^H 5 ^C 2 ^H 5 Cl CH ₂ OCH ₃ oil CH ₃ ch ₃ Cl 0 133 ^CH 3 ^C 2 ^H 5 Cl 0 c ₂ H ₅ ^C 2 ^H 5 Cl 0 98 to 99 ^CH 3 ch ₃ F 86 to 88 GH ₃ CH ₃ Cl F 114 to 116 ^GH 3 ^CH 3 Cl 00 141 to 143 GH ₃ CH ₃ Cl 94 to 97 CH ₃ ^CH 3 Cl 120 to 121

Ί continued table

r1 R ² Hal r3 Melting point CH3 ^CH 3 WHAT л> 124 to 126 c ₂ h ₅ c ₂ h ₅ WHAT 69 to 70 CH3 WHAT IN CH3 CH3 WHAT CH2-CH2OCH3 oil CH3 . CHj Cl ch (ch31och3 . oil

Example 1

A mixture of 29.2 parts by weight of 2-furancarboxylic acid N-chloromethyl-2 ^' , 6'- ^{diethylanilide} and 13.4 parts by weight of thiocyanate salt ethyl ester in 120 parts by volume of icoloyl sulphate was stirred at 25 ° C for 12 hours. After evaporation of the solvent in vacuo, the residue was taken up in ethyl acetate and water, the organic phase was dried and the solvent was combined. The residue triturated with PT diisopropylétereo 25.5 parts of N-In- m0totylarrbtol (LN-fuuyl-2-carbonyl-N ** ² '' - dietyleoiilOtometylkyyoramidu mp 101-103 ° C.

Example 2

To a solution of 12.2 parts by weight of the sodium salt of methylinkinc acid and 1 part by weight of 30 parts by volume of water is added dropwise a solution of 26.4 parts by weight at 20 to 25 ° C with vigorous phase mixing. 2-Uurancarbonyloxy acid in 70 parts by volume of methylene chloride. After stirring for six hours, the organic phase is concentrated, washed three times with water and dried over sodium sulfate. After evaporation of the solvent, 29.0 pbw of N-mono-oxo-ccrbooyl-N- (N * -fuxyrl-2-kylbenzyl-N * -2 * _> 6 (-dimethylene-10-isomethylcyclicanamide _{)) are} obtained _, which after reforming from a small amount of methanol melts at 96-98 °. C.

Example 3

24.1 parts by weight of benzoic acid N-chloromethyl-2,6-dioothyloilide are dissolved in 100 parts by volume of icetonOiril, 11.8 parts by weight of the sodium salt of kyinkirbams acid melyl ester are added and the mixture is stirred at 25 ° C for 24 hours. After insoluble materials were filtered off, the filtrate was evaporated in vacuo and the residue was dissolved in methylene chloride and water. From the organic phase, after evaporation of the solvent and recrystallization from 100 ml of methanol, 13.0 parts of N-molarcarbonyl-10 (N- * benzoyl-10 ('N2' _and 6'-dimethylamino) methyl) cyanide are isolated, m.p. 136 ° C.

The following compounds are obtained in an analogous manner:

Active substance number R ¹ R ² R ³ Melting point (° C) or n ° 1 CH 2 GH3 GH3 112 to 114 2 CHj 00 GH3 3 ^GH 3 CH3 00 4 ^GH 3 ^G 2 ^H 5 o ₂ h ₅ 5 ° ^2H 5 ^G A 00 6 GH3 ^GH3 GH (GH _{3) 2} 7 ^G2H5 00 CH _(CH3) 2 1,515 8 GH3 CH3 CH (C1) CH3 100 ALIGN! 9 CH3 00 CH (C1) CH3 10 CH3 ^GH3 CH ₂ -CH ₂ Cl oil 11 GH3 CH3 CH2-CH2-CH2Cl 12 CH3 ^G 0 CHC12 13 GH3 00 CHClg 14 GH3 GH3 CC13 15 Dec ^{GH3 G} 0 0 106 16 GH3 00 <3 17 C ^2H 5 ^G2 « ⁵ <3

continued table

Active substance number R ^{1 r2} R ³ Melting point (° C) or n = 0 18 ^CH 3 CH ₃ □ 19 Dec ^CH 3 CH ₃ 0 20 May ^C 2 ^H 5 C2H5 0 viscous substance 21 CH3 CH ₃ OH ₂ OCH ₃ 74 to 76 22nd ^C 2 ^H 5 C2H5 CH ₂ OCH 3 23 CH3 CH3 0 136 24 CH3 CH3 in F 117 25 CH3 CH ₃ 00 145 26 CH3 CH ₃ O 115 to 116 27 Mar: CH ₃ CH3 V ^x s ^z 121 28 CH3 CH3 o ^x o ^z 96 to 98

continued table

Active ingredient «810 R ¹ R ² R ³ Melting point (° C) or n * ° 29 ^C 2 ^H 5 ^C 2 ^H 5 101 to 103 30 GH ₃ C ₂ H5 CH ₂ OCH ₃ 1.5261 31 CH ₃ CH ₃ CH ₂ -CH ₃ OCH ₃ oil 32 CH ₃ CH ₃ CH _{(CH3) OCH3} oil 33 CH ₃ CH ₃ CH ₂ C1 125 to 128 34 CH ₃ ^C 2 ^H 5 CH ₂ C1 61 to 63 35 ^CH 3 CH ₃ F 136 36 CH ₃ ^CH 3 oil 37 CH ₃ CH ₃ 99

The application of the active compounds according to the invention takes the form of, for example, directly sprayable solutions, powders, suspensions, even high-percentage aqueous, oily or other suspensions, or dispersions, emulsions, oil dispersions, pastes, dusts, gritings, granules by spraying, fogging, by dusting, sprinkling or watering. The dosage forms of the compositions completely control the intended use, but in any case are intended to ensure the finest possible distribution of the active compounds according to the invention.

For the production of directly sprayable solutions, emulsions, pastes and oil dispersions, suitable are the medium to high boiling mineral oil fractions, such as kerosine or dieael oil, tar oils, etc., and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalones or derivatives thereof such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone etc., strongly polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, water, etc.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders or oil dispersions by the addition of water. For the preparation of emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent may be homogenized with wetting agents, adhesives, dispersants or emulsifiers in water. However, concentrates consisting of the active ingredient, wetting agent, adhesive, dispersant or emulsifier and optionally a solvent or oil which are suitable for dilution with water may also be prepared.

The surfactants include: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, corresponding salts of naphthalenesulfonic, phenolsulfonic, alkylarylsulfonates, alkylsulfates, alkylsulfonates, alkali metal and alkaline earth metal dibutylnaphthalenesulfonic acid salts, lauryl ether sulfate alcohols, alkali metal and alkaline earth metal fatty acid salts, sulphated hexadecanols, heptadecanols, octadecanols, sulphated fatty alcohol glycol ethers, condensation products of sulphonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene and formaldehyde naphthalenesulfone polyoxyethylenoctylphenol ethers, ethoxylated isooctylphenol-, octylphenol-, nonylphenol-, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, condensation products of fatty alcohols with ethylene oxide, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, laurylalkoholpolyglykoléteracetal, sorbitol esters, lignin, sulfite waste liquors and methylcellulose.

Powders, dusts and dusts can be used. produced by mixing or jointly grinding the active ingredients with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, are. can be produced by binding the active ingredients to solid carriers. Solid carriers are, for example, mineral clays such as silica gel, silicas, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, dust, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, magnesium oxide, ground plastics , fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as grain flours, bark meal, wood meal and nutshell meal, powdered cellulose ^O for a given ^s i ^p evné carrier ^é substances.

The new active substances show a strong fungitoxic activity against phytopathogenic fungi, in particular from the class of Phycomycetes. The new compounds are therefore suitable for instance for combating Ph ^y to ^{p and} n hthora- estans ^{f (p} LÍŠEŇ ^{b b} ram orov ^s) on tomato and Jamborách Ph ^y to ^p Phytophthora parasitica in strawberries, Phytophthora cactorum on apple, Pseudoperonospora cubensis in cucumbers, Pseudoperonospora humuli on hops, Peronospora destructor onion, Peronospora sparsa on roses, Peronospora tabacina on tobacco, Plasmopara viticola on sunflower, Sunflower Sclerospora macrospora on corn, Bremia lactucae (lettuce mold) on lettuce, Mucor mucedo on fruit and Hhizopus nigricans on beet.

The fungicidal compositions contain from 0.1 to 95% by weight of active compound, preferably from 0.5 to 90% by weight of active compound. Depending on the type of effect desired, the consumption varies between 0.1 and 5 kg of active substance per hectare.

^Ca St ^and pop sovaných employed in LATE ^{to yk} azuje ^to URAT ⁱ ve in astnostl ^l, i. whereas, in order to achieve a reliable result, the composition can be applied even after infection of the plant by the disease agent. In addition, many of the novel compounds are systemically active, so that the protection of above-ground parts of the plant can be achieved by treating the roots with such compounds.

In addition, fungi causing diseases of germinates and young whites, such as Pythium and Aphanomyces species in legumes and cotton, can also be combated with the novel compounds of the invention. Consumption ranges from 10 to 200 g of active substance per. every 100 kg of seed. In this case, the active compounds are applied as seed dressings.

The active compounds according to the invention can be present in these compositions in combination with other active compounds, such as, for example, herbicides, insecticides, growth regulators and fungicides, or they can also be mixed with fertilizers and applied in this form. When mixed with fungicides, in many cases the efficacy spectrum is expanded. Some of these fungicidal compositions also have synergistic effects, i.e. the fungicidal activity of the combination is higher than the sum of the efficacy of the individual components. A particularly favorable broadening of the spectrum of action is achieved by combining the active substances with the following fungicides:

manganese ethylenebis-dithiocarbamate, manganese-zinc ethylenebis-dithiocarbamate, zinc ammonium complex, zinc-N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthio-tetrahydrophthalimide,

N-trichloromethyl-phthalimide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-methoxycarbonylamino-benzylimidazole, 2-thiocyanatomethylthiobenzthiazole,

1,4-dichloro-2,5-dimethoxybenzene,

2,3-dichloro-6-methyl-1,4-oxathlin-5-carboxanilide,

2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide

2,4,5-trimethylfuran-3-carboxanilide, 2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxylic acid cyclohexylamide, N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide ,

5-mety1-5 viny1-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidine, 5-methyl-5-methoxymethyl-3- (3,5-dichlorfецу ^{1) '2} > 4-Dioxo-1,3-oxazolidine-Np-fluorophenyl-2,3-dichloromethylimide ·

These combinations are illustrated in more detail, but in no way limit the following list of fungicides with which the compounds of the invention may be combined.

The fungicides which may be used to combine the compounds of the invention are, for example: dithiocarbamates and derivatives thereof, such as zinc dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebis-dithiocarbamate, tetramethylthiuram disulfide,

Zinc N, N'-propylene-biB-dithiocarbamate, zinc ammoniacal complex of N, N'-propylene-bis-dithiocarbamate and N, N'-polypropylene-bls- (thiocarbamoyl) -disulfide;

nitro derivatives, such as dinitro (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethyl acrylate, 2-sec-butyl-4,6-dinitrophenylisopropyl carbonate;

hetsrocyclic compounds such as

2-Heptadecyl-2-imidazoline acetate

2,4-dichloro-6- (o-chloroanilino) -s-triazine,

O, O-diethylphthalimidophosphonothioate, 5-amino-1- [bis- (dimethylamino) foafinyl] -3-phenyl-1,2,4-triazole,

2,3-dicyano-1,4-dithiaanthraquinone,

2-thio-1,3-dithio [4,5-b] quinoxaline, t-butylcarbamoyl-2-benzimidazolecarbamic acid methyl ester,

4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thiol-1-oxide,

8-hydroxyquinoline or its copper (II) salt,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine-4,4-dioxide,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin,

2- (2-furyl) benzimidazole, piperazine-1,4-diylbis- [1- (2,2,2-trichloroethyl) formamide], 2- (4-thiazolyl) benzimidazole,

5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis- (p-chlorophenyl) pyridine-methanol,

1,2-bis- (3-ethoxycarbonyl-2-thioureido) benzene, 2-bis- (3-methoxycarbonyl-2-thioureido) benzene;

and various fungicides, such as dodecylguanidine acetate,

3- [3- (3,5-dimethyl-2-hydroxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene,

N-dichlorofluoromethylthio-N *, N * -dimethyl-N-phenyldiamide sulfuric acid,

2,5-dimethylfuran-3-carboxanilide _} 2-methylbenzoic acid anilide, 2-iodo-benzoic acid anilide,

1- (3,4-dichloroanilino) -1-formylamino-2,2,2-trichloroethane,

2,6-dimethyl-N-tridecylmorpholine and its salts,

2,6-dimethyl-N-cyclododecylmorpholine and its salts, alpha- (2-chlorophenyl) -alpha- (4-chlorophenyl) -5-pyrimidinemethanol,

1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone,

1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanol.

The fungicidal activity of the disclosed compounds is illustrated by the following examples. The following known fungicidally active compounds A and B are used as comparators in these examples.

(AND)

Example 4

Fungicidal activity against Phytophthora infestans (potato late blight) on tomatoes

The leaves of tomato plants (variety Professor Rudloff) are sprayed with aqueous suspensions containing, by weight, 80% by weight of the active substance to be tested and 20% by weight of sodium lignin sulphonate. A 0.025-0.012% spray suspension (based on dry weight) is used. After the spray coating has dried, the leaves are infected with a Phospophthora infestans zoospore suspension. The plants are then transferred to a chamber saturated with water vapor, maintaining a temperature of 16-18 ° C. After 5 days, the disease develops on untreated but infected control plants to the extent that the efficacy of the test substances can be evaluated.

The results obtained are summarized in the following overview, where they are presented using a scale of 0 to 5, where 0 means no fungal attack and 5 represents complete attack (as in the control experiment).

Active substance Infestation of the leaves after spraying with a suspension of the test compound at a cost 0.025% 0.012% 37 0 1 56 0 0 74 0 . 0 80 0 1 A (known) 2 1 kounrola (untreated) 5

Example ^ d 5

Fungicidal activity against Plasmopara viticola (vine peronoapora) on vines

The leaves of the grapevine (Muller-Thurgan species) are infected with a Plaospopara viticola zoospore suspension and the plants are kept in a water-saturated chamber (wet chamber) for 16 hours, where the temperature is maintained at 24 ° C. During this time, leaf tissue is infected. For curative activity, the plants are then sprayed with aqueous suspensions containing a total of 80% by weight of the test substance and 20% of sodium lignin sulphonate. 0.05% of the spray suspension (based on dry matter) is used. After treatment with the active substance, the vine plants are kept for 8 days in a greenhouse at a temperature of 22 to 22 ° C. Deň: 18 ° C. After this time, the plants are moved to a humid chamber for 16 hours to accelerate and intensify the sporangiophor disintegration, and the scale of the disease is evaluated using a scale of 0 to 5, where 0 means no fungal attack and 5 represents complete infestation. control plants).

The results are summarized in the table below:

Active substance Infestation of the leaves after spraying with a composition containing 0.05% of active ingredient 1 0 7 0 8 0 15 Dec 0 20 May 0 21 0 23 0 28 0 29 0 37 0 A (known) 2 to 3 inspection (untreated) 5

Example 6

Fungicidal activity against falling of pea seedlings

Stogmal samples of peas (Senator variety) are shaken vigorously in glass bottles for about 5 minutes with 300 mg (corresponding to 0.3% w / w) of the meter containing 40% dry substance and 60% clay dry matter. 100 seeds are then sewn into compote soil in seeding boxes. The seeds are sown 3 cm deep at a distance of 3 to 5 cm. The compote soil used is strongly naturally infested with Pythium spec., Aphanomrces spec., And Fusarium oxyspor. The shells are then transferred to a greenhouse at 17-20 ° C. After 21 days, the number of healthy peas was determined,

The results are summarized in the following table:

Active substance % of healthy plants after 21 days of cultivation in komopot soil 26 90 B (known) 60 control (^ treated) 10 control (srlriioioo comppoot soil) 93

EXAMPLE 7 The parts by weight of compound 1 are mixed with 10 parts by weight of N-methyl-.alpha.-pyrroloidone to give a solution which is suitable for application in the form of as small droplets as possible.

EXAMPLE 8 Parts of Compound 2 are dissolved in a basket consisting of 80 parts by weight of xylene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide per mole of N-monoethanolamide of oleic acid, 5 parts by weight of calcium dodecylbenzenesulfonic acid. 5 parts by weight of the addition product of 40 moles of ethylene oxide per mole of castor oil. Pouring and finely distributing the solution in 100,000 parts by weight of water gives an aqueous dispersion containing 0.02% by weight of the active ingredient.

Example 9 parts by weight of compound 3 span in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of addition product of 7 moles of ethylene oxide per mole of isosrylphenyl, and 10 parts by weight of addition product of 40 ml of ethylene oxide . By pouring and finely distributing the solution in 100,000 parts of water, a water dispersion is obtained which contains 0.02% by weight of the active ingredient.

Example 10 *

parts by weight of compound 1 are dissolved in a hornet consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction boiling in the range of 210 to 280 degrees Celsius and 10 parts by weight of the editorial product of 40 ml ethylene oxide per mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

Example 1.1 parts by weight of active substance 2 are intimately mixed with 3 parts by weight of diisobutylnaphthalene-alpha-sulfonic acid sodium salt, 17 parts by weight of ligninsulphonic acid sodium salt from waste sulphite lyes and 60 parts by weight of powdered silica gel, and the resulting mixture is ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray suspension is obtained which contains 0.1% by weight of active ingredient.

Example 12 parts by weight of compound 3 are intimately mixed with 97 parts by weight of finely divided kaolin. In this way, a dust containing 3% by weight of the active ingredient is obtained.

Example 13 parts by weight of compound 4 are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of the silica gel. In this way, an effective formulation with good adhesion is obtained.

EXAMPLE 14 parts by weight of active ingredient 1 are intimately mixed with 10 parts of sodium salt of the condensation product of phenolsulfonic acid, urea and formaldehyde, 2 parts of silica gel and 48 parts of water to obtain a stable aqueous dispersion, diluting with 100,000 parts by weight of water to prepare an aqueous dispersion. containing 0.04% by weight of active ingredient.

Example 15 parts of active ingredient 2 are intimately mixed with 2 parts of calcium dodecylbenzenesulfonic acid, 8 parts of polyglycol ether of fatty alcohol, 2 parts of sodium salt of phenolsulfonic acid, urea and formaldehyde condensation product and 68 parts of paraffinic mineral oil to obtain a stable oil dispersion.

Claims (1)

A fungicidal composition comprising a solid or liquid carrier and a cyanamide of the formula I-CH ₂ -N ⁴ CO-R ³ -CO-OCH ₃ -RN (I) in which: R * represents a methyl or stylish group, represents a methyl or ethyl group and represents an alkyl group having 1 to 4 carbon atoms optionally substituted by chlorine or methoxy, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group optionally substituted by fluorine, thienyl, furyl or isoxazole residue.